Tris n-alkylenepolynitro hexahydro s-triazines



3,000,889 TRIS N ALKYLENEPOLYNITRO HEXAHYDRU S-TRIAZINES Milton B.Frankel, Pasadena, Calif., assignor to Aerojetgeneral Corporation,Azusa, Califi, a corporation of re No Drawing. Filed Jan. 28, 1957, Ser.No. 636,838 16 Claims. (Cl. 260-448) This invention relates to newcompositions of matter and a method for their preparation. In particularthis invention relates to 1,3,5-triazines having the general formula:

wherein A is an alkylene radical and R is a nitro or alkyl radical.

This application is a continuation in part of my copehding United Statespatent application No. 408,608 filed February 5, 1954, now abandoned.

The compositions of this invention are useful as high explosives and canbe used in any conventional explosive missile, projectile, rocket, orthe like, as the main explosive charge. An example of such a missile isdisclosed in United States Patent No, 2,470,162, issued May 17, 1949.One way of using the high explosives of this invention in a device suchas that disclosed in United States Patent No. 2,470,162, is to pack thecrystalline explosive in powder form into the warhead of the missile.Alternatively, the crystals can be first pelletized and then packed. Acharge thus prepared is sufliciently insensitive to withstand the shockentailed in the ejection of a shell from a gun barrel or from a rocketlaunching tube under the pressure developed from ignition of apropellant charge, and can be caused to explode on operation of animpactor time fuse-mechanism firing a detonating explosive such as leadazide or mercury fulminate.

The compounds of this invention are prepared by condensing a primaryamine with formaldehyde, in accordance with the general reaction schemeset forth below:

wherein A is an alkylene radical and R is a nitro or alkyl radical.

The amines used as starting materials in this invention are prepared byreacting a strong mineral acid with a polynitro isocyanate, which may beprepared by reacting a polynitro acid halide with sodium azide, asdisclosed in assignees copending application No. 405,515, now abandoned,filed January 21, 1954.

To more fully illustrate this invention, the following examples arepresented. It is to be understood, however, that these examples arepresented merely as a means of illustration, and are not intended tolimit the scope of the invention in any way.

EXAMPLE 1 Preparation of 1,3,5-tris(3,3,3'-trinitropr0pyl)-hexahydro-1,3,5-triazine in a flask, fitted with a mechanical stirrer and droppingfunnel, was placed 34.5 gm. (0.15 mole) of 3,3,3-trinitropropyl aminehydrochloride, 75 ml. of water, and 12.1

Patented Sept. 19, 1961 gm. (0.15 mole) of sodium acetate in 50 ml. ofWater. A yellow solid was immediately precipitated, which was collected,washed with water, and dried, to give: 30.7 gm. (99.4%) of product. (Theproduct exhibited an impact stability of 9 cm./2 kg. Recrystallizationfrom a large volume of methanol gave yellow plates, M.P. 12.1123 C. dec.The elemental analysis of the product is as follows:

Calculated for C 1H N O Percent C, 23.31; percent H, 2.93; percent N,27.19. Found: Percent C, 2.3 .78; percentlH, 2.88; percent N, 27.21.

The explosive power of the compound is as follows:

Lead block value 130 T.N.T.= Ballistic mortar value 140. T.N.T.=100

EXAMPLE II Preparation of l,3,5-tri.st(3',3'-dinitr0buryl)-hexahydr0-1,3,5-triazina Twenty grn. (0.1 mole) of 3,3-dinitrobutylaminehydrochloride, 25 ml. of water, and 8.1 gm. (0.1 mole) of 37% formalinwas placed in a 300 m1. 3-necked flask, fitted with a mechanical stirrerand dropping funnel. To this solution was added dropwisea solution of8.2 gm. (0.1 mole) of sodium acetate in 15 ml. of water. A yellow solidwas immediately precipitated. After the addition was complete, stirringwas continued for an additional 30 minutes. The product was collected,washed with water, and dried; the yield was 17 gm. (97%). Tworecrystallizations from ethyl acetate yielded a product having a M.-P.of 131-132 C. (dec.), and an impact stability greater than 100 cm./2 kg.The elemental analysis of the product is as follows:

Calculated for C H N O Percent C, 34.29; per cent H, 5.18; percent N,23.99. Found: Percent C, 34.76; percent H, 5:36; percent N, 24.62.

I have also found that related amines, namely, 4,4,4- trinitrobutylamine, 3,3-dinitropentyl amine, and 4,4-dinitropentyl amine will alsocondense with formaldehyde to produce the corresponding triazines,namely, 1,3,5-tris- (4',4,4-trinitrobutyl) -hexahydro-1,3,5-triazine,1,3 ,5 -tris- (3',3'-dinitropentyl)-hexahydro-1,3,5-tria2ine, and 1,3,5-tris( 4',4-dinitropentyl -hexahydro-1,3 ,5 -tri azine.

From this it is apparent that any 1,3,5-triazine of this series can beprepared by merely condensing an appropriate intro-containing amine withformaldehyde, in accordance withthe teachings of this invention.

I claim:

1. As compositions of matter, the N-nitroalkyl-1,3,5- triazines havingthe formula:

wherein A is a lower alkylene radical and R is a radical selected fromthe group consisting of lower alkyl and 'nitro radicals.

2. As compositions of matter, the N-nitroalkyl-l,3,5- triazines havingthe formula:

wherein -A is a lower alkylene radical.

i p 3 3. As compositions of matter, the N-nitroalkyl-1,3,5- triazineshaving the formula:

wherein A is a lower alkylene radical and R is a lower alkyl radical.

4. As a composition of matter,1,3,5-tris(3',3',3'-trinitropropyl)-hexahydro-1,3,5-t1iazine, having thestructural formula:

IITO! Cg: IIQ'OI Noi-conlonr-N n-omcmcavo,

N02 CH9 OH: NO:

N NO 1 GHQ-CH: I NO:

5. As a. composition of matter,1,3,5-tris(3',3'-dinitrohutyl)-hexahydro-1,3,5-triazine, having thestructural formula:

N02 /GH2 NO: CHa-?-CHCHr-N N-CHaCHz-l -CHI NO; CH: Ha NO;

N No:

CHr-CH: I -OH:

nitropentyl)-hexahydro-1,3,5-triazine, having the structural formula:

9. The method of preparing N-nitroalkyl-l,3,5-triazines having theformula:

which comprises condensing formaldehyde with a nitrocontaining aminehaving the formula:

$02 RCANH:

wherein A is a lower alkylene radical and R is a radical selected fromthe group consisting of lower alkyl and nitro radicals.

10. The method of preparing N-nitroa1kyl-1,3,5-triazines which comprisescondensing formaldehyde with an amine having the formula:

NOz-C-A-NH:

wherein A is a lower alkylene radical.

6. As a composition of matter,l,3,5-tris(4,4',4'-trinitrobutyl)-hexahydro-1,3,5-triazine having thestructural formula:

7. As a composition of matter, 1,3,5-tris(3,3-dinitropentyl)-hex3a.hydro-1,3,-5-111iazine, having the structuralformula:

8. As a composition of matter, 1,3,5-tris(4',4'-di- 11. The method ofpreparing N-nitroalkyl-1,3,5-triazines which comprises condensingformaldehyde with an amine having the formula:

v No references cited.

1. AS COMPOSITIONS OF MATTER, THE N-NITROALKYL-1,3,5TRIAZINES HAVING THEFORMULA:
 9. THE METHOD OF PREPARING N-NITROALKYL-1,3,5-TRIAZINES HAVINGTHE FORMULA: